CN115881880A - Method for preparing metal nanocrystalline modified zinc metal negative electrode and application thereof - Google Patents
Method for preparing metal nanocrystalline modified zinc metal negative electrode and application thereof Download PDFInfo
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- CN115881880A CN115881880A CN202110998147.4A CN202110998147A CN115881880A CN 115881880 A CN115881880 A CN 115881880A CN 202110998147 A CN202110998147 A CN 202110998147A CN 115881880 A CN115881880 A CN 115881880A
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- 239000002184 metal Substances 0.000 title claims abstract description 170
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- 238000000034 method Methods 0.000 title claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000011701 zinc Substances 0.000 claims abstract description 78
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 78
- -1 metal complex ion Chemical class 0.000 claims abstract description 27
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 41
- 229910052802 copper Inorganic materials 0.000 claims description 39
- 239000010949 copper Substances 0.000 claims description 39
- 238000002360 preparation method Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 17
- 244000137852 Petrea volubilis Species 0.000 claims description 13
- 239000012459 cleaning agent Substances 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 12
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 238000011549 displacement method Methods 0.000 abstract description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- 239000002159 nanocrystal Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 15
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- 238000012360 testing method Methods 0.000 description 11
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- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- RVUXIPACAZKWHU-UHFFFAOYSA-N sulfuric acid;heptahydrate Chemical compound O.O.O.O.O.O.O.OS(O)(=O)=O RVUXIPACAZKWHU-UHFFFAOYSA-N 0.000 description 5
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- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for preparing a metal nanocrystalline modified zinc metal cathode and application thereof, belonging to the technical field of chemical synthesis. The invention provides a method for preparing a metal nanocrystalline modified zinc metal cathode, which comprises the steps of placing a pretreated zinc metal cathode in a metal complex ion solution for soaking; the method is based on a simple, low-consumption and amplifiable displacement method, the displacement reaction generation rate is effectively controlled by utilizing complexation, the zinc metal cathode modified by the metal nanocrystalline with controllable thickness is obtained, the zinc ion deposition is effectively regulated, meanwhile, the side reaction between the zinc metal and the electrolyte is effectively weakened by the metal nanocrystalline layer with chemical inertia, the stable and highly reversible zinc cathode is realized, the long cycle life and the low deposition overpotential are shown in a symmetrical battery, and the highly reversible electrochemical behavior is realized; the replacement method controlled by the complexing agent has the characteristics of simple and low-price raw materials, environmental friendliness, simplicity in operation, low energy consumption and capability of amplification, and has high application value.
Description
Technical Field
The invention relates to a method for preparing a metal nanocrystalline modified zinc metal cathode and application thereof, belonging to the technical field of chemical synthesis.
Background
Secondary batteries play an important role in daily life and the utilization of clean energy, and the demand for electronic devices and large-scale energy storage is increasing, and safer and more efficient battery technologies are required to meet various requirements.
Safe aqueous zinc ion batteries have attracted the interest of researchers. The zinc metal cathode has the advantages of high volume capacity (5855 mAh/g), high quality capacity (820 mAh/g) and low oxidation-reduction potential (-0.76V), and can be matched with various anodes; meanwhile, the abundance of zinc metal is higher than that of lithium metal, and the method has the advantage of wide resources; in addition, zinc metal and various zinc salts are environment-friendly and non-toxic, and the assembled battery has the advantage of high safety.
However, zinc metal cathodes also suffer from problems, one of which is the uneven deposition of zinc ions resulting in the creation of zinc dendrites, which can pierce the separator causing cell shorting and the creation of "dead zinc"; secondly, zinc metal is easy to generate side reactions such as corrosion, passivation and the like in the conventional zinc sulfate electrolyte, so that a large amount of gas is generated and a zinc cathode is damaged. Surface protection of zinc metal anodes is one of the effective ways to solve these problems and to advance the application of zinc anodes.
The document "chem. Eng.j.2021,416,128062" provides a method for surface protection of a zinc metal negative electrode, which realizes surface protection of the zinc metal negative electrode through a vacuum evaporation coating machine, but the method used by the method has the defects of high energy consumption, easy falling of a film layer and unsuitability for large-scale production, and the large-scale application of the method in zinc metal negative electrode protection is severely limited.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing a metal nanocrystalline modified zinc metal cathode, which comprises the following steps:
solution preparation: preparing a mixed solution of metal salt and a complexing agent to obtain a metal complex ion solution;
a pretreatment step: pretreating a zinc metal negative electrode to obtain a pretreated zinc metal negative electrode;
modification treatment: and (3) soaking the pretreated zinc metal cathode in a metal complex ion solution to obtain the metal nanocrystalline modified zinc metal cathode.
In one embodiment of the present invention, the mixed solution of the prepared metal salt and the complexing agent is: dissolving metal salt and complexing agent in deionized water.
In one embodiment of the invention, the metal nanocrystalline modified zinc metal negative electrode refers to a copper nanocrystalline modified zinc metal negative electrode; the metal salt includes at least one of copper sulfate or copper chloride.
In one embodiment of the present invention, the complexing agent comprises at least one of sodium citrate, sodium gluconate, sodium tartrate, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate salt or sodium tripolyphosphate.
In one embodiment of the present invention, in the metal complex ion solution, the molar concentration ratio of the metal salt to the complexing agent is 1 to 2, and the molar concentration of the metal salt is 0.005 to 0.1mol/L.
In one embodiment of the present invention, the pretreatment of the zinc metal negative electrode is: firstly, polishing the zinc metal cathode by using sand paper, then cleaning the zinc metal cathode by using a cleaning agent, and finally drying the zinc metal cathode;
or, the pretreatment of the zinc metal negative electrode comprises the following steps: the zinc metal cathode is placed in a dilute hydrochloric acid solution for ultrasonic treatment, then is cleaned by using a cleaning agent, and finally is dried.
In one embodiment of the present invention, the grinding of the zinc metal negative electrode using sand paper comprises: and sequentially polishing the zinc metal cathode for 5-15 min by using 2000-mesh sand paper and 4000-mesh sand paper.
In one embodiment of the present invention, the placing the zinc metal negative electrode in the dilute hydrochloric acid solution for ultrasonic processing comprises: the zinc metal cathode is placed in a dilute hydrochloric acid solution with the concentration of 0.05 to 0.15mmol/L and is subjected to ultrasonic treatment for 0.5 to 1.5min at the frequency of 50 to 150 Hz.
In one embodiment of the present invention, the cleaning of the zinc metal negative electrode with the cleaning agent comprises: and (3) cleaning the zinc metal cathode by using at least one of alcohol, acetone or deionized water, wherein each cleaning agent is used for cleaning 2-4 times.
In one embodiment of the present invention, the drying of the zinc metal negative electrode is: and drying the zinc metal negative electrode at 60-80 ℃ for 5-15 min in vacuum.
In one embodiment of the present invention, the soaking the pretreated zinc metal negative electrode in the metal complex ion solution is: soaking for 20 s-10 min under the condition of standing;
or, the step of soaking the pretreated zinc metal cathode in the metal complex ion solution is as follows: soaking for 10 s-10 min under the condition of stirring.
In one embodiment of the present invention, the rotation speed of the stirring is 50 to 600rpm.
In one embodiment of the present invention, the modification treatment step further comprises a post-treatment step; the post-treatment steps are as follows: firstly, cleaning the metal nanocrystalline modified zinc metal cathode by using a cleaning agent, and then drying the metal nanocrystalline modified zinc metal cathode.
In one embodiment of the present invention, the cleaning of the zinc metal negative electrode with the cleaning agent comprises: and respectively cleaning the metal nanocrystalline modified zinc metal cathode by using acetone, deionized water and alcohol, wherein each cleaning agent is used for cleaning 2-4 times.
In one embodiment of the present invention, the cleaning of the zinc metal negative electrode with the cleaning agent comprises: and sequentially using acetone, deionized water and alcohol to clean the metal nanocrystalline modified zinc metal cathode, wherein each cleaning agent is used for cleaning 2-4 times. And washing away excessive complexing agent ions on the surface by using acetone, washing away acetone residues by using water and alcohol, and finally easily drying by using the alcohol.
In one embodiment of the present invention, the drying the zinc metal negative electrode is: and (3) drying the metal nanocrystalline modified zinc metal negative electrode for 5-15 min at 60-80 ℃ in vacuum.
The invention also provides application of the method in preparation of the metal nanocrystalline modified zinc metal cathode.
The invention also provides a metal nanocrystalline modified zinc metal cathode, which is prepared by the method.
The invention also provides application of the metal nanocrystalline modified zinc metal cathode in assembled batteries.
The technical scheme of the invention has the following advantages:
the invention provides a method for preparing a metal nanocrystalline modified zinc metal cathode, which comprises the steps of placing a pretreated zinc metal cathode in a metal complex ion solution for soaking; the method is based on a simple, low-consumption and amplifiable displacement method, the displacement reaction generation rate is effectively controlled by utilizing complexation, the zinc metal cathode modified by the metal nanocrystalline with controllable thickness is obtained, the zinc ion deposition is effectively regulated, meanwhile, the side reaction between the zinc metal and the electrolyte is effectively weakened by the metal nanocrystalline layer with chemical inertia, the stable and highly reversible zinc cathode is realized, the long cycle life and the low deposition overpotential are shown in a symmetrical battery, and the highly reversible electrochemical behavior is realized; the replacement method controlled by the complexing agent has the characteristics of simple and low-cost raw materials, environmental friendliness, simplicity in operation, low energy consumption and capability of amplification, and has a high application value; the displacement method controlled by the complexing agent enables metal ions to form a stable complex compound through the complexing agent, and as the reduction overpotential of metal lithium is increased, the exchange current density generated by metal displacement reaction is reduced, so that a metal nanocrystalline coating with uniform and compact particles can be formed, more nucleation sites can be formed, the overpotential of zinc ion deposition is reduced, uniform deposition is induced, and the problem of zinc dendrite growth is solved; the plating layer prepared by the replacement method controlled by the complexing agent is compact and controllable in thickness, and the inert metal plating layer is stable in the electrolyte, so that the zinc metal is protected, and the hydrogen evolution reaction and corrosion can be weakened.
Drawings
FIG. 1: SEM image of copper nanocrystalline modified zinc metal negative electrode prepared in example 1.
FIG. 2 is a schematic diagram: SEM image of zinc metal negative electrode modified with copper nanocrystals obtained in example 5.
FIG. 3: constant current charge and discharge plots for the symmetric cells prepared in example 7.
FIG. 4: constant current charge and discharge plots for the symmetric cells prepared in example 8.
FIG. 5: the symmetrical cell prepared in example 9 was operated at a current density of 1mA/cm 2 Capacity of 1mAh/cm 2 Coulombic efficiency plots under conditions.
FIG. 6: comparative example 2A symmetrical cell was prepared at a current density of 1mA/cm 2 Capacity 1mAh/cm 2 Constant current charge-discharge diagram under the condition.
FIG. 7: comparative example 2A symmetrical cell was prepared at a current density of 5mA/cm 2 Capacity of 1mAh/cm 2 Constant current charge-discharge diagram under the condition.
FIG. 8: comparative example 3 asymmetric half cell at a current density of 1mA/cm 2 Capacity 1mAh/cm 2 Coulombic efficiency plots under conditions.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The following examples and comparative examples, where no specific experimental procedures or conditions are noted, can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the art. The sources of reagents, instruments and other experimental materials used in the following examples and comparative examples are shown in Table 1, and the others not indicated are all conventional products commercially available.
TABLE 1 sources of reagents, instruments and other experimental materials involved in the examples, comparative examples and test examples
Example 1: preparation of copper nanocrystalline modified zinc metal cathode
The embodiment provides a preparation method of a zinc metal cathode modified by copper nanocrystals, which comprises the following steps:
(1) Taking a commercial zinc foil with the thickness of 100 microns, grinding the commercial zinc foil for 10 minutes by using 2000-mesh sand paper, then grinding the commercial zinc foil for 10 minutes by using 4000-mesh sand paper, then cleaning the commercial zinc foil for three times by using alcohol, and drying the commercial zinc foil for 10 minutes at 70 ℃ in a vacuum oven to obtain a pretreated zinc foil;
(2) Weighing 0.5g of copper sulfate pentahydrate and 1g of sodium citrate by a balance, adding the copper sulfate pentahydrate and the sodium citrate into 500mL of deionized water, and stirring the mixture for 30 minutes on a magnetic stirrer at the rotating speed of 500rpm until the solution is uniform and is dark blue and transparent to obtain a metal complex ion solution;
(3) And (2) putting the pretreated zinc foil into a metal complex ion solution, standing for 40 seconds until the surface of the zinc foil is light yellow, taking out, washing with acetone, deionized water and alcohol sequentially for three times, and then putting into a vacuum oven to dry at 70 ℃ for 10 minutes to obtain the copper nanocrystal modified zinc metal cathode.
The above operations were carried out at normal temperature (25 ℃ C.) except for drying.
The scanning result of the copper nanocrystalline modified zinc metal cathode prepared by scanning with a scanning electron microscope is shown in figure 1.
As can be seen from FIG. 1, the diameter of the copper nanoparticles is about 100nm, the particle size is uniform, the copper nanoparticles are uniformly distributed on the surface of the zinc foil and are tightly arranged, so that the zinc ion deposition sites can be controlled, and the growth of dendrites can be relieved.
Example 2: preparation of copper nanocrystalline modified zinc metal cathode
The embodiment provides a preparation method of a zinc metal cathode modified by copper nanocrystals, which comprises the following steps:
(1) Taking a commercial zinc foil with the thickness of 100 microns, grinding the commercial zinc foil for 10 minutes by using 2000-mesh abrasive paper, then grinding the commercial zinc foil for 10 minutes by using 4000-mesh abrasive paper, then cleaning the commercial zinc foil for three times by using alcohol, and drying the commercial zinc foil for 10 minutes at the temperature of 60 ℃ in a vacuum oven to obtain a pre-treated zinc foil;
(2) Weighing 0.25g of copper sulfate pentahydrate and 0.5g of sodium citrate by a balance, adding the weighed materials into 500mL of deionized water, and stirring the mixture for 30 minutes on a magnetic stirrer at the rotating speed of 400rpm until the solution is uniform and is dark blue and transparent to obtain a metal complex ion solution;
(3) And (2) putting the pretreated zinc foil into a metal complex ion solution, standing for 40 seconds until the surface of the zinc foil is light yellow, taking out, sequentially washing with acetone, deionized water and alcohol for three times, and then putting into a vacuum oven to dry for 10 minutes at 60 ℃ to obtain the copper nanocrystal modified zinc metal cathode.
The above operations were carried out at normal temperature (25 ℃ C.) except for drying.
Example 3: preparation of copper nanocrystalline modified zinc metal cathode
The embodiment provides a preparation method of a zinc metal cathode modified by copper nanocrystals, which comprises the following steps:
(1) Adding commercial zinc foil with the thickness of 100 micrometers into dilute hydrochloric acid (0.1 mmol/L), performing ultrasonic treatment for 1 minute at 100Hz, taking out, washing with deionized water and alcohol for three times respectively, and drying in a vacuum oven at 80 ℃ for 10 minutes to obtain pretreated zinc foil;
(2) Weighing 0.25g of copper sulfate pentahydrate and 0.5g of sodium citrate by a balance, adding the copper sulfate pentahydrate and the sodium citrate into 500mL of deionized water, and stirring the mixture for 30 minutes on a magnetic stirrer at the rotating speed of 350rpm until the solution is uniform and is dark blue and transparent to obtain a metal complex ion solution;
(3) And (2) putting the pretreated zinc foil into a metal complex ion solution, standing for 40 seconds until the surface of the zinc foil is light yellow, taking out, sequentially washing with acetone, deionized water and alcohol for three times, and then putting into a vacuum oven to dry for 10 minutes at 80 ℃ to obtain the copper nanocrystal modified zinc metal cathode.
The above operations were carried out at normal temperature (25 ℃ C.) except for drying.
Example 4: preparation of copper nanocrystalline modified zinc metal cathode
The embodiment provides a preparation method of a zinc metal cathode modified by copper nanocrystals, which comprises the following steps:
(1) Taking a commercial zinc foil with the thickness of 100 microns, grinding the commercial zinc foil for 10 minutes by using 2000-mesh sand paper, then grinding the commercial zinc foil for 10 minutes by using 4000-mesh sand paper, then cleaning the commercial zinc foil for three times by using alcohol, and drying the commercial zinc foil for 10 minutes at 75 ℃ in a vacuum oven to obtain a pretreated zinc foil;
(2) Weighing 0.5g of copper sulfate pentahydrate and 1.2g of sodium citrate by a balance, adding the weighed materials into 500mL of deionized water, and stirring the mixture for 30 minutes on a magnetic stirrer at the rotating speed of 350rpm until the solution is uniform and is dark blue and transparent to obtain a metal complex ion solution;
(3) And (2) putting the pretreated zinc foil into a metal complex ion solution, standing for 40 seconds until the surface of the zinc foil is light yellow, taking out, sequentially washing the zinc foil with acetone, deionized water and alcohol for three times, and then putting the zinc foil into a vacuum oven to dry for 10 minutes at 75 ℃ to obtain the copper nanocrystal modified zinc metal cathode.
The above operations were carried out at normal temperature (25 ℃ C.) except for drying.
Example 5: preparation of copper nanocrystalline modified zinc metal cathode
The embodiment provides a preparation method of a zinc metal cathode modified by copper nanocrystals, which comprises the following steps:
(1) Taking a commercial zinc foil with the thickness of 100 microns, grinding the commercial zinc foil for 10 minutes by using 2000-mesh sand paper, then grinding the commercial zinc foil for 10 minutes by using 4000-mesh sand paper, then cleaning the commercial zinc foil for three times by using alcohol, and drying the commercial zinc foil for 10 minutes at 65 ℃ in a vacuum oven to obtain a pretreated zinc foil;
(2) Weighing 0.5g of copper sulfate pentahydrate and 1g of sodium citrate by a balance, adding the copper sulfate pentahydrate and the sodium citrate into 500mL of deionized water, and stirring the mixture for 30 minutes on a magnetic stirrer at the rotating speed of 500rpm until the solution is uniform and is dark blue and transparent to obtain a metal complex ion solution;
(3) And (2) putting the pretreated zinc foil into a metal complex ion solution, standing for 10 minutes until the surface of the zinc foil is yellow, taking out, quickly washing with acetone, deionized water and alcohol for three times in sequence, and then putting into a vacuum oven to dry for 10 minutes at 65 ℃ to obtain the copper nanocrystal modified zinc metal cathode.
The above operations were carried out at normal temperature (25 ℃ C.) except for drying.
The scanning result of the copper nanocrystalline modified zinc metal cathode prepared by scanning with a scanning electron microscope is shown in figure 2.
As can be seen from fig. 2, after the standing time of the zinc foil in the metal complex ion solution is increased, the size of the copper nanoparticles generated on the surface of the zinc foil is increased, the arrangement is tighter, and the layer thickness is increased, which proves that the thickness of the metal nanocrystal modification layer can be controlled simply by adjusting the reaction time.
Example 6: preparation of copper nanocrystalline modified zinc metal cathode
The embodiment provides a preparation method of a zinc metal cathode modified by copper nanocrystals, which comprises the following steps:
(1) Taking a commercial zinc foil with the thickness of 100 microns, grinding the commercial zinc foil for 10 minutes by using 2000-mesh sand paper, then grinding the commercial zinc foil for 10 minutes by using 4000-mesh sand paper, then cleaning the commercial zinc foil for three times by using alcohol, and drying the commercial zinc foil for 10 minutes at 70 ℃ in a vacuum oven to obtain a pretreated zinc foil;
(2) Weighing 0.5g of copper nitrate and 1g of sodium citrate by a balance, adding the copper nitrate and the sodium citrate into 500mL of deionized water, and stirring the mixture for 30 minutes on a magnetic stirrer at the rotating speed of 500rpm until the solution is uniform and is dark blue and transparent to obtain a metal complex ion solution;
(3) And (2) putting the pretreated zinc foil into a metal complex ion solution, standing for 40 seconds until the surface of the zinc foil is light yellow, taking out, sequentially washing the zinc foil with acetone, deionized water and alcohol for three times, and then putting the zinc foil into a vacuum oven to dry for 10 minutes at 70 ℃ to obtain the copper nanocrystal modified zinc metal cathode.
The above operations were carried out at normal temperature (25 ℃ C.) except for drying.
Comparative example 1: preparation of zinc metal cathode
The present comparative example provides a method of making a zinc metal anode, the method comprising the steps of:
a commercial zinc foil with a thickness of 100 micrometers was taken, ground with 2000-mesh sandpaper for 10 minutes, then ground with 4000-mesh sandpaper for 10 minutes, and then washed with alcohol three times, and dried in a vacuum oven at 70 ℃ for 10 minutes to obtain a zinc metal negative electrode.
The above operations were carried out at normal temperature (25 ℃ C.) except for drying.
Example 7: symmetric battery containing copper nanocrystalline modified zinc metal cathode and preparation thereof
The embodiment provides a symmetrical battery containing a zinc metal cathode modified by copper nanocrystals, and the preparation method comprises the following steps:
the copper nanocrystalline modified zinc metal negative electrode obtained in example 1 was cut into 11mm diameter wafers by a cutting machine, used as a working electrode and a counter electrode, and a symmetrical battery (adv. Mater.2021, 2101649) was assembled in the order of 2032 positive electrode case, counter electrode, separator, working electrode, gasket, spring plate, 2032 negative electrode case, using Celgard separator, electrolyte was a 2mol/L heptahydrate sulfuric acid solution.
The constant current charge and discharge performance of the symmetrical battery obtained by the assembly is tested by a Xinwei battery tester, and the battery test conditions are as follows: current density 1mA/cm 2 Capacity of 1mAh/cm 2 The test results are shown in FIG. 3.
As can be seen from figure 3, the symmetrical battery using the zinc foil modified by the copper nanocrystals maintains stable cycle and keeps a lower over-potential at about 30mV in 500h, and the modification layer is proved to be capable of reducing the energy barrier of zinc ion deposition and have an excellent protection effect on zinc metal.
Example 8: symmetric battery containing copper nanocrystalline modified zinc metal cathode and preparation thereof
The embodiment provides a symmetrical battery containing a zinc metal cathode modified by copper nanocrystals, and a preparation method of the symmetrical battery comprises the following steps:
the copper nanocrystalline modified zinc metal negative electrode obtained in example 4 was cut into 11mm diameter wafers by a cutting machine, and used as a working electrode and a counter electrode, symmetrical batteries were assembled in the order of 2032 positive electrode case, counter electrode, separator, working electrode, gasket, spring plate, and 2032 negative electrode case, using Celgard separator, and the electrolyte was a 2mol/L heptahydrate sulfuric acid solution.
The constant current charge and discharge performance of the symmetrical battery obtained by the assembly is tested by a Xinwei battery tester, and the battery test conditions are as follows: current density 1mA/cm 2 Capacity of 1mAh/cm 2 The test results are shown in FIG. 4.
As can be seen from fig. 4, at higher current density, the modified electrode has high reversibility and stability, and the assembled symmetric cell can be stably cycled for 800h.
Example 9: asymmetric half-cell containing copper nanocrystalline modified zinc metal negative electrode and preparation thereof
The embodiment provides an asymmetric half-cell containing a zinc metal cathode modified by copper nanocrystals, and the preparation method comprises the following steps:
the copper nanocrystalline-modified zinc metal negative electrode obtained in example 4 was cut into a 11 mm-diameter wafer by a dicing machine, and used as a working electrode, a symmetric battery was assembled in the order of a 2025 positive electrode case, a copper foil, a separator, a working electrode, a gasket, a spring plate, and a 2025 negative electrode case, using a Celgard separator, and an electrolyte was a 2mol/L heptahydrate sulfuric acid solution.
The coulomb efficiency of the asymmetric half-cell obtained by assembling the new power cell tester is tested by the new power cell tester, and the cell test conditions are as follows: current density 1mA/cm 2 Capacity of 1mAh/cm 2 The test results are shown in FIG. 5.
As can be seen from FIG. 5, the current density was 1mA/cm 2 Under the current density of the copper nano-crystal modified zinc metal negative electrode, the overall coulombic efficiency of the modified zinc metal negative electrode is stable in 700 cycles, and the average coulombic efficiency reaches 99.7 percent, so that the copper nano-crystal modified zinc metal negative electrode is proved to have high deposition/removal reversible performance.
Comparative example 2: symmetrical battery containing zinc metal cathode and preparation thereof
This comparative example provides a symmetric cell containing a zinc metal negative electrode, prepared as follows:
the zinc metal negative electrode obtained in comparative example 1 was cut into a wafer of 11mm in diameter by a cutting machine, and used as a working electrode and a counter electrode, and a symmetrical battery was assembled in the order of 2032 positive electrode case, counter electrode, separator, working electrode, gasket, spring plate, and 2032 negative electrode case, using Celgard separator, and the electrolyte was a 2mol/L heptahydrate sulfuric acid solution.
The constant current charge and discharge performance of the symmetrical battery obtained by the assembly is tested by a Xinwei battery tester, and the battery test conditions are as follows: current density 1mA/cm 2 Capacity 1mAh/cm 2 And a current density of 5mA/cm 2 Capacity of 1mAh/cm 2 The test results are shown in FIGS. 6 to 7.
As can be seen from fig. 6 to 7, the symmetrical batteries assembled by using the unmodified zinc metal negative electrode all show shorter cycle life and larger overpotential with larger overpotential fluctuation under different current densities, indicating that the unmodified zinc metal negative electrode has poor reversible performance and unstable interface.
Comparative example 3: asymmetric half-cell containing zinc metal negative electrode and preparation thereof
The present comparative example provides an asymmetric half-cell containing a zinc metal negative electrode, prepared as follows:
the zinc metal negative electrode obtained in comparative example 1 was cut into a wafer having a diameter of 11mm by a cutter, and a symmetrical battery was assembled in the order of 2025 positive electrode case, copper foil, separator, working electrode, gasket, spring plate, and 2025 negative electrode case as a working electrode, using Celgard separator, and electrolyte was a heptahydrate sulfuric acid solution having a concentration of 2 mol/L.
The coulomb efficiency of the asymmetric half-cell obtained by assembling the new power cell tester is tested by the new power cell tester, and the cell test conditions are as follows: current density 1mA/cm 2 Capacity 1mAh/cm 2 The test results are shown in FIG. 8.
As can be seen from FIG. 8, the current density was 1mA/cm 2 Under the current density of the zinc alloy anode, the average coulombic efficiency of the unmodified pure zinc metal anode is low in 66-week cycle, low deposition/removal reversible performance is shown, and the coulombic efficiency is greatly fluctuated after 66 weeks, so that the fact that the surface of the zinc metal anode is damaged is proved, and low stability in the cycle is shown.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.
Claims (10)
1. A method for preparing a metal nanocrystalline modified zinc metal anode is characterized by comprising the following steps:
solution preparation: preparing a mixed solution of metal salt and a complexing agent to obtain a metal complex ion solution;
a pretreatment step: pretreating the zinc metal cathode to obtain a pretreated zinc metal cathode;
modification treatment: and (3) soaking the pretreated zinc metal cathode in a metal complex ion solution to obtain the metal nanocrystalline modified zinc metal cathode.
2. The method of claim 1, wherein the metal nanocrystalline-modified zinc metal anode is a copper nanocrystalline-modified zinc metal anode; the metal salt includes at least one of copper sulfate or copper chloride.
3. The method of claim 1 or claim 2, wherein the complexing agent comprises at least one of sodium citrate, sodium gluconate, sodium tartrate, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, or sodium tripolyphosphate.
4. The method according to any one of claims 1 to 3, wherein the molar concentration ratio of the metal salt to the complexing agent in the metal complex ion solution is 1 to 2, and the molar concentration of the metal salt is 0.005 to 0.1mol/L.
5. The method of any of claims 1 to 4, wherein the zinc metal negative electrode is pretreated by: firstly, polishing the zinc metal cathode by using sand paper, then cleaning the zinc metal cathode by using a cleaning agent, and finally drying the zinc metal cathode;
or, the pretreatment of the zinc metal negative electrode comprises the following steps: the zinc metal cathode is placed in a dilute hydrochloric acid solution for ultrasonic treatment, then is cleaned by using a cleaning agent, and finally is dried.
6. The method of any one of claims 1 to 5, wherein the immersing the pre-treated zinc metal negative electrode in the metal complex ion solution is: soaking for 20 s-10 min under the condition of standing;
or, the step of soaking the pretreated zinc metal cathode in the metal complex ion solution is as follows: soaking for 10 s-10 min under the condition of stirring.
7. The method of any one of claims 1 to 6, wherein the modification treatment step is followed by a post-treatment step; the post-treatment steps are as follows: firstly, cleaning the metal nanocrystalline modified zinc metal cathode by using a cleaning agent, and then drying the metal nanocrystalline modified zinc metal cathode.
8. Use of the method of any one of claims 1 to 7 for the preparation of a metal nanocrystalline modified zinc metal anode.
9. A metal nanocrystalline-modified zinc metal negative electrode, characterized in that the metal nanocrystalline-modified zinc metal negative electrode is prepared by the method of any one of claims 1 to 7.
10. Use of the metal nanocrystalline modified zinc metal anode of claim 9 in an assembled battery.
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| US20080156652A1 (en) * | 2006-12-28 | 2008-07-03 | Chang Gung University | Cyanide-free pre-treating solution for electroplating copper coating layer on zinc alloy surface and a pre-treating method thereof |
| CN108242560A (en) * | 2017-12-26 | 2018-07-03 | 深圳先进技术研究院 | Zinc-base Dual-ion cell and preparation method thereof |
| CN111900388A (en) * | 2020-05-26 | 2020-11-06 | 北京理工大学 | Zinc ion battery negative electrode material, preparation and application thereof |
| CN112331933A (en) * | 2020-10-27 | 2021-02-05 | 华中科技大学 | Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof |
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| US20080156652A1 (en) * | 2006-12-28 | 2008-07-03 | Chang Gung University | Cyanide-free pre-treating solution for electroplating copper coating layer on zinc alloy surface and a pre-treating method thereof |
| CN108242560A (en) * | 2017-12-26 | 2018-07-03 | 深圳先进技术研究院 | Zinc-base Dual-ion cell and preparation method thereof |
| CN111900388A (en) * | 2020-05-26 | 2020-11-06 | 北京理工大学 | Zinc ion battery negative electrode material, preparation and application thereof |
| CN112331933A (en) * | 2020-10-27 | 2021-02-05 | 华中科技大学 | Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof |
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